CN114835558A - Preparation process of 2,3,5, 6-tetrafluoro terephthalyl alcohol - Google Patents
Preparation process of 2,3,5, 6-tetrafluoro terephthalyl alcohol Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 74
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 40
- IWKPBYPUIPVYNZ-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-dimethylbenzene Chemical group CC1=C(F)C(F)=C(C)C(F)=C1F IWKPBYPUIPVYNZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000746 purification Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 7
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 41
- 229940125782 compound 2 Drugs 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 229940126214 compound 3 Drugs 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 229940125904 compound 1 Drugs 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000007810 chemical reaction solvent Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000012025 fluorinating agent Substances 0.000 claims description 6
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 5
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZFHGXWPMULPQSE-SZGBIDFHSA-N (Z)-(1S)-cis-tefluthrin Chemical compound FC1=C(F)C(C)=C(F)C(F)=C1COC(=O)[C@@H]1C(C)(C)[C@@H]1\C=C(/Cl)C(F)(F)F ZFHGXWPMULPQSE-SZGBIDFHSA-N 0.000 description 1
- CTSQZGJZQUVGBQ-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3,6-dimethylbenzene Chemical group CC1=C(Cl)C(Cl)=C(C)C(Cl)=C1Cl CTSQZGJZQUVGBQ-UHFFFAOYSA-N 0.000 description 1
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000005939 Tefluthrin Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DDVNRFNDOPPVQJ-HQJQHLMTSA-N transfluthrin Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=CC(F)=C1F DDVNRFNDOPPVQJ-HQJQHLMTSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
- C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
Abstract
The invention discloses a preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol, which comprises the steps of synthesizing an esterified group through alcoholysis of cyano group at para position on a benzene ring, reducing ester to hydroxyl, and fluorinating substituent groups at other positions on the benzene ring to obtain the 2,3,5, 6-tetrafluoro-p-xylene glycol; the preparation process has relatively simple production process operation, simple reactions such as alcoholysis, reduction, fluorination and the like are carried out, the reaction production period is short, the reaction is stable, and the amplification production is facilitated; no waste gas is generated, and the steps of tail gas treatment are reduced; the raw materials are cheap and easy to obtain, the yield is improved, and the product cost is favorably reduced; the product and by-products and impurities generated in the reaction process are easy to purify and separate, the impurities can be removed from the product without a complex purification process, the actual application standard of high purity can be achieved, the product preparation process is simplified, the product purity is high, the yield and quality requirements of large-scale application can be met, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol.
Background
The 2,3,5, 6-tetrafluoro terephthalyl alcohol is an important intermediate for organic synthesis, and can be used for synthesizing tefluthrin and transfluthrin as pesticides, synthesizing parylene oxide as a novel coating material and the like. The price of 2,3,5, 6-tetrafluoro-p-xylene glycol is relatively expensive, but the literature on synthesizing 2,3,5, 6-tetrafluoro-p-xylene glycol is few, so that the search for a new optimized synthesis method of 2,3,5, 6-tetrafluoro-p-xylene glycol is of great significance.
Patents GB2127013A, EP1247792B1, CN1458137A, WO2005035474, etc. provide a synthesis method of 2,3,5, 6-tetrafluoroterephthalyl alcohol. But tetrafluoroterephtalic acid and its derivatives, such as acid chloride, aldehyde, ester, etc., are synthesized and reduced to produce tetrafluoroterephthalyl alcohol. The route is most applied at present and is put into industrial production, but has the defects that the tetrafluoro terephthalic acid raw material is difficult to obtain, a large amount of waste water and waste gas are generated in the synthetic process, the environment is not friendly, the activity of the raw material is high, and the reaction has certain danger.
Patent WO2002002504 provides a new synthesis concept, which comprises reducing tetrafluoroterephthalonitrile as a raw material to tetrafluorop-xylylenediamine, and hydrolyzing to obtain a product after diazotization reaction by using sodium nitrite. The reduction reaction condition of the route is harsh, the diazotization reaction is not easy to control, and the number of byproducts is large, so that the product yield is not high, and therefore, the optimization is needed.
Chinese patent CN106431833A provides a preparation route of tetrafluoroterephthalonitrile, which comprises introducing dry hydrogen chloride gas into tetrafluoroterephthalonitrile as a raw material and methanol as a solvent to prepare tetrafluoroterephthaloyl imino ester, preparing dimethyl tetrafluoroterephthaloyl by hydrolysis, and finally preparing tetrafluoroterephthaloyl alcohol by hydrogen reduction in an autoclave. The route is low in cost and short in route, but the defects that dry hydrogen chloride gas is difficult to obtain, a large amount of hydrogen chloride gas escapes in the reaction process to generate acid waste gas, and a large amount of acid waste water is difficult to treat after the reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the preparation process of the 2,3,5, 6-tetrafluoro-p-xylene glycol, and the preparation process has the advantages of relatively simple production process operation, short reaction production period, stable reaction, no waste gas generation and contribution to large-scale production; the raw materials are cheap and easy to obtain, the yield is improved, and the product cost is favorably reduced; therefore, the method is suitable for industrial production.
The purpose of the invention can be achieved by adopting the following technical scheme:
a preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol is characterized by comprising the following steps:
preparation step S1: reacting the compound 1 with an esterification reagent to prepare a compound 2;
preparation step S2: reacting the compound 2 with a reducing reagent to prepare a compound 3;
preparation step S3: reacting the compound 3 with a fluorination reagent to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol;
wherein, the structural formula of the compound 1 is a general structure shown in a formula I:
compound 2 formula is represented by formula II:
the structure formula of the compound 3 is a general structure of a formula III:
wherein X is halogen; r is saturated or unsaturated, straight-chain or branched C 1 -C 30 One of the hydrocarbon groups;
wherein the reaction formula of the preparation step S1 is described by formula (1):
wherein the reaction formula of the preparation step S2 is described by formula (2):
wherein the reaction formula of the preparation step S3 is described by formula (3):
further, when X in compound 1 is F, 2,3,5, 6-tetrafluoroterephthalyl alcohol is obtained through preparation step S1 and preparation step S2.
Further, in the preparation step S1, the esterifying reagent is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol.
Further, in the step S2, the reducing agent is at least one of sodium borohydride, lithium aluminum hydride, potassium borohydride, hydrogen, zinc powder, and stannous chloride.
Further, in the step S3, the fluorinating agent is at least one of sodium fluoride, potassium fluoride, hydrofluoric acid, and anhydrous hydrogen fluoride.
Further, in the preparation step S1, the reaction temperature is 30-140 ℃, the reaction pressure is 0-2MPa, and the reaction time is 3-18 hours;
in the preparation step S2, the reaction temperature is 30-140 ℃, the reaction pressure is 0-2MPa, and the reaction time is 3-18 hours;
in the preparation step S3, the reaction temperature is 30-140 ℃, the reaction pressure is 0-2MPa, and the reaction time is 3-18 hours.
Further, the molar ratio of the compound 1 to the esterifying reagent in the preparation step S1 is 1: (1-8); the molar ratio of the compound 2 to the reducing agent in the preparation step S2 is 1: (1-8); the molar ratio of the compound 3 to the fluorinating agent in the preparation step S3 is 1: (1-8).
Further, in the preparation step S1, the compound 1 is reacted with an esterification reagent in a reaction solvent a, where the reaction solvent a is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, and dimethyl sulfoxide;
in the preparation step S2, reacting the compound 2 with a reducing agent in a reaction solvent B, wherein the reaction solvent B is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide and dimethyl sulfoxide;
in the preparation step S3, the compound 3 is reacted with a fluorinating agent in a reaction solvent C, wherein the reaction solvent C is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide and dimethyl sulfoxide.
Further, the method also comprises the following preparation steps:
under the dry condition, the obtained crude 2,3,5, 6-tetrafluoro-p-xylene glycol is dissolved in a purifying solvent by using a dry closed device or under the blowing of dry gas, and then recrystallization and drying are carried out to obtain the refined 2,3,5, 6-tetrafluoro-p-xylene glycol.
Further, the purifying solvent is one or a combination of more than two of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide and dimethyl sulfoxide
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation process of the 2,3,5, 6-tetrafluoro-p-xylene glycol, an esterification group is synthesized through alcoholysis of cyano group at para position on a benzene ring, then ester reduction is carried out to obtain hydroxyl, and substituent groups at other positions on the benzene ring are fluorinated to obtain the 2,3,5, 6-tetrafluoro-p-xylene glycol; the preparation process has relatively simple production process operation, simple reactions such as alcoholysis, reduction, fluorination and the like, short reaction production period and stable reaction, and is beneficial to large-scale production; no waste gas is generated, and the steps of tail gas treatment are reduced; the raw materials are cheap and easy to obtain, the yield is improved, and the product cost is favorably reduced; therefore, the method is suitable for industrial production.
The product obtained by the preparation method of the invention is easy to purify and separate from byproducts and impurities generated in the reaction process, and the product can remove the impurities without a complex purification process, thereby reaching the actual application standard of high purity, simplifying the preparation process of the product, leading the product to have high yield and high purity, and meeting the requirements of large-scale application on yield and quality.
Detailed Description
The present invention will be further described with reference to the following embodiments, which are not intended to limit the scope of the present invention, but are defined by the following examples, which are provided for illustration of the principles of the present invention; that is, the following description is only a part of the preferred embodiment of the present invention, and it is not intended to limit the scope of the present invention, and it will be apparent to those skilled in the art that various changes, modifications and variations can be made in the present invention without departing from the spirit, principle and scope of the invention, additional features of the invention may be included alone or in any combination, and these changes, modifications and variations should also be considered to be within the scope of the claimed invention. In addition, the raw materials used in the invention are generally common commercial products, so that the sources of the raw materials do not need to be specifically limited.
Purity was calculated by nuclear magnetic purity: nuclear magnetic analysis was performed using a Bruker (AVANCE 400 mega, Bruker corporation) nuclear magnetic resonance spectrometer.
The pressure values mentioned in this patent application, if not specified otherwise, are gauge pressures, and gauge pressures refer to the total absolute pressure exceeding the ambient atmospheric pressure or the pressure at a point in the liquid above atmospheric pressure.
The yield, as a percentage ratio of actual product mass to theoretical product mass, and theoretical product mass, were calculated as the raw materials in the reaction equation were not in excess.
Example 1
A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol comprises the following preparation steps:
(1) the preparation step 1:
reacting 1 mol of compound 1 with methanol in a reactor to prepare a compound 2; the solvent is methanol, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 20 hours, after the reaction is finished, the mixture is cooled, saturated sodium bicarbonate water solution is added, the mixture is filtered, extracted by ethyl acetate and dried by spinning, and the compound 2 is obtained, wherein the conversion rate is 65 percent.
(2) The preparation step 2:
in a reactor, 1 mol of compound 2 in the formula is reacted with sodium borohydride to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol; the molar ratio of the compound 2 to the sodium borohydride is 1: 3; the solvent is tetrahydrofuran, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 3 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the 2,3,5, 6-tetrafluoro-p-xylene glycol is obtained, wherein the yield is 90%.
(3) A purification step 3:
in a reactor, 1 mol of crude 2,3,5, 6-tetrafluoro terephthalyl alcohol is purified by taking methanol as a solvent, insoluble substances are removed by suction filtration, filtrate is subjected to rotary evaporation to remove the solvent, refined products are obtained, and the purification yield is 90%.
H-NMR(400MHz，rt，DMSO-D6)：δ＝4.87(s，4H)，7.85(s，2H)；C-NMR(400MHz，rt，DMSO-D6)：δ＝57.5，128.5，139.7。
Example 2
A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol comprises the following preparation steps:
(1) the preparation step 1:
reacting 1 mol of compound 1 in the formula with methanol in a reactor to prepare compound 2; the solvent is methanol, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 20 hours, after the reaction is finished, the mixture is cooled, saturated sodium bicarbonate water solution is added, the mixture is filtered, extracted by ethyl acetate and dried by spinning, and the compound 2 is obtained, wherein the conversion rate is 70%.
(2) The preparation step 2:
reacting 1 mol of compound 2 with sodium borohydride in a reactor to prepare a compound 3; the molar ratio of the compound 2 to the sodium borohydride is 1: 3; the solvent is THF, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 3 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the compound 3 is obtained, wherein the yield is 90%.
(3) A preparation step 3:
reacting 1 mol of compound 3 with potassium fluoride in a reactor to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol; the molar ratio of the compound 3 to the potassium fluoride is 1: 8; the solvent is DMF, the reaction temperature is 120 ℃, the reaction pressure is normal pressure, the reaction time is 7 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the 2,3,5, 6-tetrafluoro-p-xylene glycol is obtained with the yield of 74 percent.
(4) And 4, a purification step:
in a reactor, 1 mol of crude 2,3,5, 6-tetrafluoro terephthalyl alcohol is purified by acetone as a solvent, insoluble substances are removed by suction filtration, and the solvent is removed by rotary evaporation of filtrate to obtain a refined product with the purification yield of 97%.
H-NMR(400MHz，rt，DMSO-D6)：δ＝4.86(s，4H)，7.28(s，2H)；C-NMR(400MHz，rt，DMSO-D6)：δ＝51.8，118.5，145.7。
Example 3
A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol comprises the following preparation steps:
(1) the preparation step 1:
reacting 1 mol of compound 1 in the formula with ethanol in a reactor to prepare compound 2; the solvent is ethanol, the reaction temperature is 90 ℃, the reaction pressure is normal pressure, the reaction time is 20 hours, after the reaction is finished, the mixture is cooled, saturated sodium bicarbonate water solution is added, the mixture is filtered, extracted by ethyl acetate and dried by spinning, and the compound 2 is obtained, wherein the conversion rate is 73 percent.
(2) The preparation step 2:
reacting 1 mol of compound 2 with potassium borohydride in a reactor to prepare a compound 3; the molar ratio of the compound 2 to the potassium borohydride is 1: 3; the solvent is THF, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 3 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the compound 3 is obtained, wherein the yield is 89%.
(3) A preparation step 3:
reacting 1 mol of compound 3 with sodium fluoride in a reactor to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol; the molar ratio of the compound 3 to the sodium fluoride is 1: 8; the solvent is DMF, the reaction temperature is 120 ℃, the reaction pressure is normal pressure, the reaction time is 7 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the 2,3,5, 6-tetrafluoro-p-xylene glycol is obtained with the yield of 81 percent.
(4) And 4, a purification step:
in a reactor, 1 mol of crude 2,3,5, 6-tetrafluoro p-xylene glycol is purified by using ethanol as a solvent, insoluble substances are removed by suction filtration, filtrate is subjected to rotary evaporation to remove the solvent, refined 2,3,5, 6-tetrafluoro p-xylene glycol is obtained, and the purification yield is 98%.
H-NMR(400MHz，rt，DMSO-D6)：δ＝4.69(s，4H)，7.38(s，2H)；C-NMR(400MHz，rt，DMSO-D6)：δ＝54.2，121.5，136.7。
Example 4
A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol comprises the following preparation steps:
(1) the preparation step 1:
reacting 1 mol of compound 1 in the formula with ethanol in a reactor to prepare compound 2; the solvent is ethanol, the reaction temperature is 90 ℃, the reaction pressure is normal pressure, the reaction time is 17 hours, after the reaction is finished, the mixture is cooled, saturated sodium bicarbonate water solution is added, the mixture is filtered, extracted by ethyl acetate and dried by spinning, and the compound 2 is obtained, wherein the conversion rate is 78%.
(2) The preparation step 2:
reacting 1 mol of compound 2 with lithium aluminum hydride in a reactor to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol; the molar ratio of the compound 2 to the lithium aluminum hydride is 1: 3; the solvent is tetrahydrofuran, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 1 hour, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the 2,3,5, 6-tetrafluoro-p-xylene glycol is obtained with the yield of 91%.
(3) And (3) a purification step:
in a reactor, 1 mol of crude 2,3,5, 6-tetrafluoro-p-xylene glycol is purified by dimethyl carbonate as a solvent, insoluble substances are removed by suction filtration, and the solvent is removed by rotary evaporation of filtrate to obtain refined 2,3,5, 6-tetrafluoro-p-xylene glycol with the purification yield of 94%.
H-NMR(400MHz，rt，DMSO-D6)：δ＝4.79(s，4H)，7.35(s，2H)；C-NMR(400MHz，rt，DMSO-D6)：δ＝52.1，114.5，139.7。
Example 5
A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol comprises the following preparation steps:
(1) the preparation step 1:
reacting 1 mol of the compound 1 in the formula with n-amyl alcohol in a reactor to prepare a compound 2; the solvent is n-amyl alcohol, the reaction temperature is 110 ℃, the reaction pressure is normal pressure, the reaction time is 12 hours, after the reaction is finished, the mixture is cooled, saturated sodium bicarbonate aqueous solution is added, the mixture is filtered, extracted by ethyl acetate and dried by spinning, and the compound 2 is obtained, wherein the conversion rate is 74 percent.
(2) The preparation step 2:
reacting 1 mol of compound 2 with stannous chloride in a reactor to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol; the molar ratio of the compound 2 to the stannous chloride is 1: 3; the solvent is tetrahydrofuran, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 3 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the 2,3,5, 6-tetrafluoro-p-xylene glycol is obtained with the yield of 91%.
(3) And (3) a purification step:
in a reactor, 1 mol of crude 2,3,5, 6-tetrafluoro p-xylene glycol is purified by using methanol as a solvent, insoluble substances are removed by suction filtration, filtrate is subjected to rotary evaporation to remove the solvent, and refined 2,3,5, 6-tetrafluoro p-xylene glycol is obtained, wherein the purification yield is 92%.
H-NMR(400MHz，rt，DMSO-D6)：δ＝4.78(s，4H)，7.31(s，2H)；C-NMR(400MHz，rt，DMSO-D6)：δ＝55.8，120.5，142.5。
Example 62, 3,5, 6-tetrachloroterephthalyl alcohol preparation Process
A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol comprises the following preparation steps:
(1) the preparation step 1:
reacting 1 mol of compound 1 with isopropanol in a reactor to prepare a compound 2; the solvent is isopropanol, the reaction temperature is 135 ℃, the reaction pressure is normal pressure, the reaction time is 17 hours, after the reaction is finished, the mixture is cooled, saturated sodium bicarbonate water solution is added, the mixture is filtered, extracted by ethyl acetate and dried by spinning, and the compound 2 is obtained, wherein the conversion rate is 81%.
(2) The preparation step 2:
reacting 1 mol of compound 2 with zinc powder in a reactor to prepare a compound 3; the molar ratio of the compound 2 to the zinc powder is 1: 3; the solvent is THF, the reaction temperature is 80 ℃, the reaction pressure is normal pressure, the reaction time is 3 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the compound 3 is obtained, wherein the yield is 90%.
(3) The preparation step 3:
reacting 1 mol of compound 3 with hydrofluoric acid in a reactor to prepare 2,3,5, 6-tetrachloroterephthalyl alcohol; the molar ratio of the compound 3 to the hydrofluoric acid is 1: 8; the solvent is DMF, the reaction temperature is 120 ℃, the reaction pressure is normal pressure, the reaction time is 7 hours, after the reaction is finished, the solvent is removed by rotation, ethyl acetate is added, the mixture is washed twice by water, anhydrous sodium sulfate is dried, then the ethyl acetate is removed by rotation, and the 2,3,5, 6-tetrachloro-p-xylene glycol is obtained with the yield of 95%.
(4) And 4, a purification step:
in a reactor, 1 mol of crude 2,3,5, 6-tetrachloroterephthalyl alcohol is purified by taking methanol as a solvent, insoluble substances are removed by suction filtration, filtrate is subjected to rotary evaporation to remove the solvent, and refined 2,3,5, 6-tetrachloroterephthalyl alcohol is obtained, wherein the purification yield is 97%.
H-NMR(400MHz，rt，DMSO-D6)：δ＝4.82(s，4H)，7.27(s，2H)；C-NMR(400MHz，rt，DMSO-D6)：δ＝52.8，115.5，143.7。
The experiment shows that the 2,3,5, 6-tetrachloroterephthalyl alcohol prepared in the embodiment has high purity and low impurity content, and can meet the requirements of the application field, and the conversion rate of the preparation step 1 of the preparation method can reach more than 65 percent and can reach 81 percent at most; the yield of the step 2 can reach 90%, the yield of the fluorination step can also reach over 74% and can reach 95% at most, and the yield of the purification step can reach over 90% and can reach 98% at most.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation process of 2,3,5, 6-tetrafluoro-p-xylene glycol is characterized by comprising the following steps:
preparation step S1: reacting the compound 1 with an esterification reagent to prepare a compound 2;
preparation step S2: reacting the compound 2 with a reducing reagent to prepare a compound 3;
preparation step S3: reacting the compound 3 with a fluorination reagent to prepare 2,3,5, 6-tetrafluoro-p-xylene glycol;
wherein, the structural formula of the compound 1 is a general structure shown in a formula I:
compound 2 formula is represented by formula II:
the structure formula of the compound 3 is a general structure of a formula III:
wherein X is halogen; r is saturated or unsaturated, straight-chain or branched C 1 -C 30 One of the hydrocarbon groups.
2. The process of claim 1, wherein when X is F in compound 1, 2,3,5, 6-tetrafluoroterephthalyl alcohol is prepared through the steps of S1 and S2.
3. The process of any one of claims 1-2, wherein in step S1, the esterifying reagent is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol.
4. The process according to any one of claims 1 to 2, wherein in step S2, the reducing agent is at least one of sodium borohydride, lithium aluminum hydride, potassium borohydride, hydrogen, zinc powder, and stannous chloride.
5. The process of claim 1, wherein in step S3, the fluorinating agent is at least one of sodium fluoride, potassium fluoride, hydrofluoric acid, and anhydrous hydrogen fluoride.
6. The process according to any one of claims 1 to 2, wherein in the step S1, the reaction temperature is 30 to 140 ℃, the reaction pressure is 0 to 2MPa, and the reaction time is 3 to 18 hours;
in the preparation step S2, the reaction temperature is 30-140 ℃, the reaction pressure is 0-2MPa, and the reaction time is 3-18 hours;
in the preparation step S3, the reaction temperature is 30-140 ℃, the reaction pressure is 0-2MPa, and the reaction time is 3-18 hours.
7. The process according to any one of claims 1 to 2, wherein the molar ratio of compound 1 to the esterifying reagent in the preparation step S1 is 1: (1-8); the molar ratio of the compound 2 to the reducing agent in the preparation step S2 is 1: (1-8); the molar ratio of the compound 3 to the fluorinating agent in the preparation step S3 is 1: (1-8).
8. The process according to any one of claims 1 to 2, wherein in step S1, compound 1 is reacted with an esterification reagent in a reaction solvent a, wherein the reaction solvent a is one or a combination of two or more selected from methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, and dimethyl sulfoxide;
in the preparation step S2, the compound 2 and the reducing agent react in a reaction solvent B, where the reaction solvent B is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, and dimethyl sulfoxide;
in the preparation step S3, the compound 3 is reacted with a fluorinating agent in a reaction solvent C, wherein the reaction solvent C is one or a combination of two or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide and dimethyl sulfoxide.
9. The process according to any one of claims 1 to 8, wherein the process further comprises the following steps:
under the dry condition, the obtained crude 2,3,5, 6-tetrafluoro-p-xylene glycol is dissolved in a purifying solvent by using a dry closed device or under the blowing of dry gas, and then recrystallization and drying are carried out to obtain the refined 2,3,5, 6-tetrafluoro-p-xylene glycol.
10. The process according to claim 9, wherein the purification solvent is one or a combination of two or more selected from methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, and dimethylsulfoxide.
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